Regiodivergent Hydrosilylation of Polar Enynes to Synthesize Site‐Specific Silyl‐Substituted Dienes.

Herein, we present catalyst‐regulated switchable site‐selective hydrosilylation of enynes, which are suitable for a wide range of alkyl and aryl substituted polar enynes and exhibit excellent functional group compatibility. Under the optimized conditions, silyl groups can be precisely installed at various positions of 1,3‐dienes. While α‐ and γ‐silylation products were obtained under platinum‐catalytic systems, β‐silylation products were delivered with [Cp*RuCl]4 as catalyst. This process lead to the formation of 1,3‐dienoates with diverse substitutions, which would pose challenges with other methodologies. [ABSTRACT FROM AUTHOR]